Silicones for

Coatings & Inks

Market Segmentation – Sub Markets

3 market sub-segments
• Industrial Paints
(High and Medium Temp, foul release, Resin Intermediates)

• Food Release Paint

(Bakery trays coating system)

• Paints Additives
(Ind Paints, Leather Coating, Printing Inks, Pigment treatment)
Industrial Paints
Preamble -Basic Glossary
Painting is the act of coating an object for decorative and/or
protective purposes and requires:

• A substrate suitable to receive the coating

• A coating suitable for the selected substrate
• An application cycle suitable for a proper coating

Combination of three conditions above allows to get the required

performances being purely decorative either protective

First criteria of distinction between coatings is:

Varnish
Binder + Solvent and possibly color.
After drying the coating is transparent. Color is always soluble in
the varnish and it must not be confused with a pigment.
Liquid Paint
Binder + Solvent + Pigment+ Filler (optionally) + Additives.
Also existing solventless liquid paints and solids paints (powders)
Preamble - Basic Glossary
Components and functions of a coating are

Binder: base component of a coating; it’s a polymer that after drying

and/or curing becomes a solid layer bringing adhesion and protection
on the substrate.

Solvent: ingredient that allow to apply the coating onto the substrate;
as soon as it’s made the job it has to evaporate. Possible also to have
coating solvent free (solventless or powder)

Pigment: insoluble powder used to make the coating opaque, colored,

and mask the substrate. Might also have protective function

Filler: mainly used to improve coverage & impart matte finish.

Additives: used in small amount additives can cover many functions:

surface wetting, pigment dispersion, levelling, defoaming, slip,
adhesion, texturing, catalyst.
Binders for Industrial Coating

• Binders are the main ingredients of a paint . A binder covers in

between 20 to 50% of the total weight of the formulation even
more when the paint’s dry.
• Binders impart chemical, mechanical, protective performances
and drive the aesthetic of the coating.
• Chemical composition and choice of a binder depends on the
final application of a coatings; in the following table a short
summary of the most commons binders and related
performances.
 Main Binders for Industrial Coating
Weather Chemical
Binder Curing Cond Aesthetic Application
Resistance resistance
Good (High Construction Agro
Air Alkyl Air Oxygen Medium Medium
gloss) Machinery
In oven (with Auto , Tractors
Oven Alkyl Good Good Good
amino res) met. furniture
Polyester In oven (with
Excellent Excellent Good Auto, Fridge, Coil
(saturated) amino res)
Acrylic (OH, In Oven (with amino Good/Excellent Medium/Good Good/Excellent Dom Appliance
Carboxy, Amido) or expoxy res)

Poor
Excellent (especially
Epoxy Amino Catalyst Medium crumbling Protective, Marine
solvents and alkaly)
yellowing
Isocyanate react with Bodywork, wood
Polyurethanes Polyester OH
Excellent Good Excellent
furniture
Nitrocellulosic Physical drying Good Medium Poor Wood furniture
Good If
Vinyl Physical drying Good Medium Protective, Marine
high thickness
Globally good but
High and Medium
Mostly air drying alkali, some acid,
Temp, Dielectrical,
Silicones but need to be Good Excellent and some solvent
Protective (top
heat cured when not fully
coat)
cured
Silicones Resins
Silicone resins Chemistry
Branched linked caged structures composed of D, T-
functional or MQ functional units
• Durable, thermally stable, UV stable
• Various degrees of flexibility and
inertness
• Enhance weatherability, water repellency,
physical strength & release properties
• Compatible with a wide range of organics
• Solvent-based or solvent-less forms
• Can be formulated into aqueous systems

R R R R R O O O
Si Si Si Si
R O O O O O O O

R3SiO1/2 R2SiO2/2 RSiO3/2 SiO4/2

M D T Q
 Silicone resins Chemistry
R R R R R O O O
Si Si Si Si
R O O O O O O O

R3 SiO1/2 R2 SiO2/2 RSiO3/2 SiO4/2

M D T Q
For the most common silicone resins R might be Methyl or Phenyl group.

A resin network has also reactive functions that generally are silanol (-OH)
or methoxy (OCH3) groups needed to build up the network and increase the
molecular weight; commercial product as supplied are much more
«oligomer/pre-polymer» of low molecular weight; in this status resins
don’t have the necessary cohesion to act as binder. Once solvent
evaporates film start forming by condensation of reactive group below
mechanism accordingly:

Si – OH + HO – Si Si – O – Si + H2 O

Methyl Groups (Me) bring water repellency, release, incompatibility with

organic products, hardness but also fragility

Phenyl Groups (ɸ) bring thermal resistance, Thermoplasticity, flexibility,

compatibility with organic products, chemical resistance
Silicone resins Chemistry
Depending on possible blends of functional units, producers can obtain
several resins structures. A kind of modelisation useful to understand resins
properties (f) of their structure on the diagram below, where on:
• Y axes R/Si = CH3/Si + ɸ/Si ratio can range from 1 to 2 and
(ratio close to 2 means more linear structure)
• X axes is the ratio ɸ/Si ranging from 0 to 1
(typically max one Phenyl group per atom of silicon)

R/Si = Me/Si + ɸ/Si

2

Release
Thermoplasticity

Flexibility
Hydrophobicity Compatibility

Thermal Stability

Fragility Hardness

Air drying Oven drying

Reactivity
ɸ/Si
1
0 1
Silicone resins range in aromatic solvent

Max.
% Resin
Product Type Temp( Application
solid hardness
°C)
Anti corrosion
BSR SR 379 Me 50 600 Hard
Heat Resistance
Heat resistant
BRB SR 379 N Me 50 600 Anti corrosion Hard
Bit softer than 379
Low viscosity
Heat resistant,
BRB SR 383 Me, Phe. 50 650 Medium
Anti-corrosion
High Temperature
Anti Corrosion
BRB SR 313 Me, Phe. 80 650 Medium
High solids
Low VOC
 Silicone Alkoxy Oligomer

Product Type % solid Application

Alone as a resin: Room Temperature moisture curing

(need catalyst/curing agent) coatings ( short tack dry
time, high hardness and excellent water-repellency ( high
temperature paints up to 600-650°C, auto body coating,
floor coatings etc)

As Organic Resin Modifier (especially Water based)

BSR SR 833 Methyl
100% Add typical silicones features (weatherability, Water-
(ind scale up) Alkoxy
repellency, Heat Resistance) to those belonging to organic
polymer. Major application:
- Acrylic (construction material coatings)
- Polyester (industrial, high temp operating appliances)
- Epoxy (anti stain, anti corrosive paints)
- Alkyd (storage tankers, external structures)
Pigment, Driers, Formulation
Paint formulations
Ingredients selection criteria
• In general we consider heat resistant paints all those paints that
must work in continuous service temperature ranging from 200
to 650° C with nor or limited discoloration and no any loss of
adhesion.

• Main critieria used to select the most appropriate binder are

continuous service temperature and service temperature film
hardness. In case of low and medium service temperature paints
producers might use hybrid system (silicone - modified organic)
where the amount of silicone resin is higher when service
temperature increase. Pure Silicones resins system are required
for the highest service temperature.
Paint formulations
Ingredients selection criteria

• Softer Silicones resins are typically selected for the highest

service temperature whilst harder resins are used for less
extreme temperature when hot hardness is required.

• Also pigment will be chosen in functon of the service

temperature requirements. Standard colored pigment are
generally suitable for formulation not exceeding 350 – 400 °C;
for higher temperatures only heat stable pigments should be
used; aluminum paste, metal oxides (iron, manganese ) and
ceramics pigment (see tables next page)
 Paint formulations Ingredients selection criteria
Service Temperature Usueful Binder Pigment selection
100 – 200 °C Silicone -modified Organic All Pigments possible
200 – 320 °C Silicone- modified Organic Aluminum
Colored Pigment
320 – 420 °C Silicone or Colored ,Black,Aluminum,
Organic-modified silicones (Sil/Pet –Sil Epoxy) Zinc
420 – 530 °C Silicone Colored, Aluminum
530 – 650 °C Silicone Black Aluminum
650 to about 750°C Silicone Ceramic

Silicones Resins – Suitable pigments/Filler (f) service Temp (°C)

800

Ceramic FeMn/oxide Mica

700 MiOx TiO2, Color
Zinc
600 Dust
Clear
500 Me/Phenyl

400
Clear
300 Aluminum Methyl

200

100
Paint formulations
Ingredients selection criteria
• Silicones Resin are thermostable products. When used as varnish
their long term (thousand of hours) continuous thermal resistance
is about 250°C with no any film degradation. Above 250°C
degradation of methyl then of phenyl group progressively start
and above 550°C we get a polysilicon layer fully mineral.

• This mechanism is the basic of high temperature resistant paint

where in presence of Aluminum paste and Zinc dust (the
pigments) a reaction between the polysilicic acid and the metal
occur with formation of a polysilicate layer highly cohesive and
highly adhesive on the substrate.

• Third party studies demonstrated that despite its volatility, zinc

dust is really helpful to enhance the performance of the aluminum
Paint formulations
Ingredients selection criteria
Driers
• To achieve optimum properties silicone paints need to be cured
especially when the paint works at very high temperature or
when it is submitted to thermal shocks; if resin is under cured
film is generally softer with poor adhesion and lower corrosion
and chemical resistance.
• Curing, when possible, is achieved through a curing cycle when
the paint is heated in between 200°C – 300°C (lower temp for
the pure methyl resins – higher temp for the Me/Phenyl resins)
for 1 hour. Is typically recommended to increase progressively
the curing temperature to avoid blistering.
• Addition of metallic driers (Fe, Zinc, or Cobalt Octoate)
improve the cure rate of the paints and reduce their
thermoplasticity
Food Release Application
Silicone resins range in aromatic solvent
Food Release Application
Max.
Resin
Product Type % solid Temp(°C Application
hardness
)

Non stick Coatings

BSR SR 385 FD Me, Ph 50% 300 Medium
(Bakery Pans , Toaster, BBQs)

Silicone resins are easier to coat (one step cycle) than silicone elastomers
as well as PTFE (multi step process). Number of baking can be extended
provided an accurate pre-treatment Re-coating is also less expensive than
for the other technologies
Methyl Phenyl Silicones Resins, in general, are not really suitable for high
fat-high sugar content products. Silicones Elastomers or PTFE coatings
provide better performances in this case.
Additives
 BRB – Additive Range (in progress)

Function BRB Offer Status

Sample
Substrate Wetting BRB Siloen WA 260 Available

Substrate Wetting BRB Siloen WA 261 Commercial

Sample
Substrate Wetting BRB Siloen WA 263 Available

Sample
Substrate Wetting BRB Siloen WA 264 Available
 BRB – Additive Range ( in progress)
Function BRB Offer Status

Levelling Flow BRB Siloen LA 271 Commercial Q1 2017

Sample
Slip, Mar Resistance BRB Siloen SMA 280 Available

Sample
Slip, Mar Resistance BRB Siloen SMA 283 Available

Sample
Slip, Mar Resistance BRB Siloen SMA 284 Available

Sample
Slip, Mar Resistance BRB Siloen SMA 285 Available

Sample
Slip, Mar Resistance BRB Siloen SMA 286 Available
 BRB – Additive Range ( in progress)

Function BRB Offer Status

Sample
Defoamer BRB Siloen DA 290 Available

BRB Siloen TA 394 Already Commercial

Texturing Additive
(Hammertone Additive) former PA 394

Pigment Dispersant Sample

(also for plastic appl)
BRB Siloen PDA 222 Available

For more information, please consult the

Paint Additives User Guide
 BRB – Additive Range ( in progress)

Function BRB Offer Status

Commercial
Adhesion Promoter Silanil 250

Adhesion Promoter Silanil 919 Commercial

Adhesion Promoter Silanil 176 Commercial

Adhesion Promoter Silanil 258 Commercial

Adhesion Promoter Silanil 581 Commercial

Silanes for Zinc-Rich Coating
Functions of Silanes in Zinc-Rich Coating
Zinc-rich coating typically contains 60-95% metallic zinc in dry film
for purpose of corrosion (cathodic) protection which may be classified
into 2 types.
Zinc-rich Coating

Organic Zinc-rich Coating Inorganic Zinc-rich Coating

Silane as Coupling Agent

Silanil 176, 138,
Based on Based on
Alkali Metal Silicate Alkyl Silicate Binders
919, 258
Binders

Silane as Crosslinker Silane as Binder

Silanil 118 Silanil 781

http://www.galvanizeit.org

Slides or internal training only

I. Organic zinc-rich coating :
Zinc particles are encapsulated by organic binder (waterborne or solvent
borne) such as
> Epoxy-amine
> Epoxy-polyamide
> Phenoxy
> Polyurethane
> Vinyl
> Chlorinated rubber

Silane monomer or oligomer (partially

hydrolysed) is post-added in the formulation.

http://www.duluxprotectivecoatings.com.au/
II. Inorganic zinc-rich coating
(zinc silicate coating) :
There are 2 types of binders, alkali metal silicate and alkyl silicate.
Zinc particles are able to chemically react with these binders and silicate
based binder can chemically react with steel substrate.

e.g. Potassium silicate

+ Silanil118
+ Zinc dust
II. Inorganic zinc-rich coating
(zinc silicate coating) :

Typical Formulation of
Zinc-rich Ethyl Silicate (Silanil 781)

“Cured zinc
silicate film”

Ref: Parashar, G., Srivastava, D., and Kumar,

P. Progress in Organic Coatings 42 (2001) 1-14.
Customer Chain for Zinc-Rich Coating
Resin Paint
End Product
Manufacturers Manufacturers

• Epoxy
• Polyurethane Organic Inorganic
• Vinyl Zinc-rich Zinc-rich

Coupling Agent Coupling Agent Crosslinker Binder

Silanil138,176, Silanil138,176,
Silanil118 Silanil781
919,258 919,258

Picture Ref. : http://www.galvanizeit.org

Recommendation in Zinc-Rich Coating
Inorganic zinc-rich coating
Organic zinc-rich coating Alkali Metal Silicate Alkyl Silicate (TES40)
Silanil176 Silanil 118 Silanil 781 (Si40)
Silanil138
Silanil258
(Up to type of resins)
Remarks : Recommendation based on testing and historical experience data.